9H-Dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepines

ABSTRACT

IN WHICH N IS DEFINED ABOVE, R7 and R8 are each selected from the group consisting of hydrogen and alkyl as defined above, or   TOGETHER IS PYRROLIDINO OR PIPERIDINO; WHEREIN R2 is selected from the group consisting of hydrogen, alkyl, defined as above, hydroxymethyl,   IN WHICH N&#39;&#39; IS 0 TO 4, INCLUSIVE, AND R is hydrogen or alkyl defined as above or R2 is   IN WHICH N&#39;&#39; IS DEFINED AS ABOVE, AND R7 and R8 are each selected from the group consisting of hydrogen and alkyl as defined above, or   TOGETHER IS PYRROLIDINO, OR PIPERIDINO; WHEREIN R3 and R4 are selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, alkyl, defined as above, trifluoromethyl, and alkoxy, in which the carbon moiety is of 1 to 3 carbon atoms, inclusive, are prepared by reacting a thio compound of formula 1   D R A W I N G     wherein R1 is selected from the group consisting of hydrogen, alkyl of 1 to 3 carbons, inclusive,   IN WHICH N IS 1 TO 4, INCLUSIVE, AND R is hydrogen or alkyl defined as above, or R1 is   D R A W I N G WHEREIN R3 and R4 are defined as above, with formic acid hydrazide or, in two steps, with hydrazine and then triethylorthoformate. The resulting products 11 can be further modified to yield the other compounds corresponding to formula III, as defined above. Compounds of formula III and the pharmacologically acceptable acid addition salts and N-oxides thereof have central nervous system antidepressant activity and can be used in mammals and birds. Compounds of the formula III:

United States Patent Hester, Jr. et al.

[451 May 27, 1975 9H-DIBENZO(B,F )-S-TR1AZOLO(4,3-

1))(1 ,4)DIAZEPINES [75] Inventors: Jackson B. Hester, ,lr., Galesburg;

Jacob Szmuszkovicz, Kalamazoo, both of Mich.

[731 Assignee: The Upjohn Company, Kalamazoo,

Mich.

[22] Filed: Feb. 11, 1974 [21] Appl. No.: 441,107

Related U.S. Application Data [63] Continuation-impart of Ser. No.313,208, Dec. 8, I972, Pat. No. 3,850,942, which is acontinuation-in-part of Ser. No. 277,916, Feb. 22, I972, abandoned.

[52] U.S. Cl 260/308 R; 71/92; 260/239 DD; 260/239.3 T; 260/246 B;260/247.l E;

260/247.5 D; 260/247.5 EP; 260/268 PC; 260/293.59; 260129361; 424/248,424/269;

[51] Int. CL. C07d 57/02; C07d 57/04; C07d 99/02 [58] Field of Search260/308 R, 246 B, 247.1 E, 260/247.5 D, 247.5 EP1268 PC, 293.59, 293.61

References Cited FOREIGN PATENTS OR APPLICATIONS 2,306,762 8ll973Germany 260/308 R Primary ExaminerAlton D. Rollins Attorney, Agent, orFirm-Hans L. Berenis [57] ABSTRACT Compounds of the formula III:

wherein R is selected from the group consisting of hydrogen, alkyl of lto 3 carbons, inclusive,

in which n is I to 4, inclusive, and R is hydrogen or alkyl defined asabove, or R. is

in which n is O to 4, inclusive, and R is hydrogen or alkyl defined asabove or R is l in which n' is defined as above, and R and R, are eachselected from the group consisting of hydrogen and alkyl as definedabove, or

together is pyrrolidino, or piperidino', wherein R and R, are selectedfrom the group consisting of hydrogen, fluoro, chloro, bromo, nitro,alkyl, defined as above, trifluoromethyl, and alkoxy, in which thecarbon moiety is of l to 3 carbon atoms, inclusive, are prepared byreacting a thio compound of formula I wherein R and R, are defined asabove, with formic acid hydrazide or, in two steps, with hydrazine andthen triethylorthoformate. The resulting products II can be furthermodified to yield the other compounds corresponding to formula III, asdefined above.

Compounds of formula III and the pharmacologically acceptable acidaddition salts and N-oxides thereof have central nervous systemantidepressant activity and can be used in mammals and birds.

19 Claims, No Drawings 1 9H-DIBENZO(B,F)-S-TRIAZOLO(4,3- D )(l,4)DIAZEPINES CROSS-REFERENCE TO RELATED APPLICATIONS This applicationis a continuatiomin-part of application Ser. No. 3 I 3.208 filed Dec. 8.1972, now US. Pat No 3.850.942 which is a continuation-in-part ofapplication Ser. No. 227,9l6 filed Feb. 22. 1972. now abandoned.

BACKGROUND OF THE INVENTION Field of the Invention This invention isdirected to new organic compounds and is particularly concerned withnovel compounds of formulae [1 and Ill and processes for the productionthereof.

The novel compounds and the process of production therefore can beillustratively represented as follows:

wherein R, is selected from the group consisting of hydrogen, alkyl of lto 3 carbon atoms. inclusive.

in which n is l to 4, inclusive, and R is hydrogen or alkyl defined asabove, or R, is

in which n is defined as above, and R and R are each selected from thegroup consisting of hydrogen and alkyl as defined above. or

together is pyrrolidino, or piperidino; wherein R is selected from thegroup consisting of hydrogen. hydroxymethyl. alkyl defined as above,

in which n is 0 to 4, inclusive, and R is hydrogen or alkyl defined asabove, or R is in which n is defined as above, and R and R are eachselected from the group consisting of hydrogen and alkyl as definedabove or wherein R, is selected from the group consisting of hydrogen.alkyl of l to 3 carbon atoms, inclusive.

in which n is l to 4, inclusive, and R is hydrogen or alkyl defined asabove, or R is in which n is defined as above, and R and R are eachselected from the group consisting of hydrogen and al kyl, as definedabove, or

together is pyrrolidino or piperidino', wherein R is selected from thegroup consisting of hydrogen, hydroxymethyl, alkyl, as defined above,

and I CnHz l T N N in which n is U to 4, inclusive, and R is hydrogen oralkyl defined as above, or R is in which n' is defined as above, and R;and R,, are each selected from the group consisting of hydrogen andalkyl as defined above. or

wherein R, is selected from the group consisting of hydrogen, methyl,ethyl,

in which n, is l to 3, inclusive, and R is hydrogen, or alkyl of l to 3carbon atoms. inclusive, or R, is

in which n is defined as above, R and R are selected from the groupconsisting of hydrogen and alkyl as defined above, or

together is pyrrolidino or piperidino; wherein R: is selected from thegroup consisting of hydrogen, alkyl, as defined above,

in which n,,' is 0 to 3. inclusive, and R and R,, are each selected fromthe group consisting of hydrogen and alkyl as defined above, or

together is pyrrolidino or piperidino; wherein R: and R, are selectedfrom the group consisting of hydrogen, fluoro, bromo, chloro, nitro.

The most desirable compounds of formula III are those of the formulalllB:

in which n is l to 3, inclusive, and R and R are hydrogen, methyl orethyl, or

together is pyrrolidino; wherein R" is selected from the groupconsisting of hydrogen, methyl, ethyl,

in which n is defined as above, and R" and R" are each selected from thegroup consisting of hydrogen, methyl and ethyl; wherein R";, and R" areselected from the group consisting of hydrogen, fluoro or chloro.

The invention also embraces the pharmacologically acceptable acidaddition salts and N-oxides of the compounds of formula III above.

The process of this invention comprises: heating a thio compound offormula l with formic acid hydrazide or hydrazine andtriethylorthoformate to obtain the triazole compound ll. Compound [llcan be obtained by heating a thio compound of formula I with a selectedcarboxylic acid hydrazide of 2 to 4 carbon atoms, inclusive, orhydrazine and a carboxylic halide of the formula wherein R is definedabove and X is chloro or bromo.

DESCRIPTION OF THE PREFERRED EMBODIMENT Lower alkyl groups of l to 3carbon atoms, inclusive, are exemplified by methyl, ethyl. propyl andisopropyl.

The carbon chain moiety of alkoxy is of l to 3 carbon atoms, inclusive,and therefore defined as loweralkyl of l to 3 carbon atoms. inclusive.

The group CnH n wherein n is l to 4 comprises -CH2 '(CH2)2 2):t' 'i"-(CH2)4*- and branched alkylene such as:

The compounds of formula III and the pharmacologically acceptable acidaddition salts are useful central nervous system agents for the controlof depression and anxiety in mammals and birds.

For the control of depression the compounds of formula Ill and thepharmacologically acceptable acid addition salts can be used in unitdosages of 0.l to 5.0 mg./kg. in oral or injectable preparations toalleviate depression occurring in stressful situations in the samemanner as imipramine, amitriptylene and other antidepressants. Suchsituations are those, for example, when animals are changing ownershipor are temporarily put into kennels while their owners are absent fromhome.

For the control of anxiety the compounds of formula III and thepharmacologically acceptable acid addition salts can be used in unitdosages of 0.1 to 10 mg./kg. in oral and injectable preparations toalleviate tension and anxiety in mammals or birds in the same way asdoxepine and other antianxiety agents. Such stressful situations arise,for example, when animals are in travel.

Acid addition salts of the compounds of formula III can be made, such asthe fluosilicic acid addition salts which can be applied as mothproofingagents, and salts with trichloroacetic acid, useful as herbicidesagainst Johnson grass, Bermuda graas, yellow and red foxtail, and quackgrass.

The pharmaceutical forms of compounds of formula Ill and salts thereofcontemplated by this invention include pharmaceutical compositionssuited for oral, parenteral, and rectal use, e.g., tablets, powderpackets, cachets, dragees, capsules, solutions, suspension, sterileinjectable forms, suppositories, bougies, and the like. Suitablediluents or carriers such as carbohydrates, lactose, proteins, lipids,calcium phosphate, cornstarch, stearic acid, methylcellulose and thelike may be used as carriers or for coating purposes. Water or oils suchas coconut oil, sesame oil, safflower oil, cottonseed oil, and peanutoil, may be used for prepar ing solutions or suspensions of the activedrug. Sweetening, coloring, and flavoring agents may be added.

For mammals food premixes with starch, oatmeal, dried fishmeat,fishmeal, flour, and the like can be prepared,

The starting materials of this invention dihydrodibenzoazepinethiones Iare either known or can be synthesized by known procedures eg. byrefluxing the corre sponding amides with phosphorus pentasulfide, asfurther illustrated in the Preparations.

In carrying out the process of this invention, a selected thione I, isheated with a carboxylic acid hydrazide to about 200 for a period of 30minutes to 4 hours. Product III which is thus obtained, is isolated andpurified by conventional means, e.g. extraction. fil tration,chromatography or crystallization.

Alternatively the thione-starting material I can be treated withhydrazine or hydrazine hydrate at temperatures between 25-100 C. with orwithout a solvent such as ethanol or other alkanol, ether,tetrahydrofuran, benzene or the like for l to 4 hours to give thecorresponding intermediate 1V:

wherein R and R are defined as above, compound 1V can be condensed withan acid halide of the formula R al-i1 wherein R: is defined as R;hereinabove, when n is 1-4, and X" is bromo or chloro to give thecorrespond ing compound of formula 111.

If ethyl orthoformate is used, a 3-unsubstituted 9H-dibenzo[c,f]-s-triazolo[4,3-a1diazepine, is obtained which can bebrominated and the resulting bromo compound can be used as intermediatefor additional 3- substituted compounds of formula III as shown in theExamples.

The following preparations and examples are illustrative of theprocesses and products of the present invention. but are not to beconstrued as limiting.

PREPARATION l 5,10-Dihydro-l1H-dibenzo[b,e][1,4]diazepine-11 thione Amixture of 5,10-dihydro-llH-dibenzo[b,e][1,4- ]diazepin-l l-one (10 g.,0.0476 mole), phosphorus pentasulfide (9.3 g., 0.0525 mole) and 365 ml.of pyridine was heated at reflux temperature for 3 hours and allowed tostand overnight. The pyridine was evaporated, and the residue was shakenwith 250 ml. each of water and chloroform. The resulting suspension wasfiltered to remove solid product. After filtration the chlo roform layerwas separated from the aqueous layer, washed with water and saturatedsalt solution. dried over anhydrous magnesium sulfate and evaporated.The residue was combined with the solid obtained above and crystallizedfrom methanol. Two crops of 5,-10-dihydro1lH-dibenzo[b,e]{1,4]diazepin-1l-thione were obtained; yield,9.01 g. (84% of theory), melting point 257-259 C.

PREPARATlON 2 7-Ch1oro-5.10-dihydro-1lH-dibenzolb,e]-

11.4]diazepine-1l-thione A mixture of7ch1oro-5,10-dihydro-1lH-dibenzolb- ,e}-{l.4]diazepin-l l-one (30.5 g.,0.125 mole), phosphorus pentasulfide (27.8 g, 0.131 mole) and one l. ofpyridine was heated at reflux temperature for 4 hours and the pyridinewas evaporated in vacuo. The residue was stirred for I hour with one 1.each of saturated aqueous sodium bicarbonate and methylene chloride andfiltered to remove some solid product. The organic layer of the filtratewas washed successively with sodium bicarbonate solution and withsaturated salt solution, dried over anhydrous magnesium sulfate andevaporated. The residue was combined with the solid obtained above andtriturated with hot chloroform and methanol; 12.2 g. of7-chloro-5,l0-dihydro-1 1H- dibenzo[h,e][1,4]diazepine-1 l-thione wasobtained of melting point 274-275 C. Concentration of thechloroform-methanol washings afforded an additional 8.4 g. of producthaving the same melting point. Recrystallization fromdimethylformamide-water gave an analytical sample in the form of paleyellow needles of melting point 276277 C.

PREPARATION 3 5, 1 0-Dihydro-5-methyl-1 1H-dibenzo[ b,e

1 1 ,4ldiazepine-l l-thione A mixture of 5.10-dihydro-5-methyl-l1H-dibenzo[b- ,e]-{1,4]diazepin-11-one (6.1 g., 0.0272 mole), phosphoruspentasulfide (6.5] g., 0.0286 mole) and ml. of pyridine was heated atreflux temperature for 3.75 hours and the pyridine was then evaporatedin vacuo. The residue was shaken with chloroform and saturated aqueoussodium bicarbonate. The resulting suspension was filtered to give solidA. The chloroform layer of the filtrate was washed successively withsaturated aqueous sodium bicarbonate and with saturated salt solution,dried over anhydrous magnesium sulfate, and evaporated. The residue wascrystallized from methylene chloride-methanol to give 3.5 g. of5,10-dihydro-5- methyl-1lH-dibenzo[b,e][1,4]diazepin-l l-thione; ofmelting point 217-218 C., which was unchanged after recrystallization. Asecond crop weighed 0.8 g. and melted at 214215 C. A third crop weighed0.25 g. and melted at 216217.

Solid A was shaken with methylene chloride and 10% sodium hydroxide andprocessed as above to give an additional 1.5 g. melting at 2162 17 C.

Anal. calcd. for C H N S: C, 69.96; H, 5.03; N. 11.66; S, 1334. Found:C, 69.79; H, 5.02; N, 11.37; S, 13.29.

EXAMPLE 1 3-Methyl-9Hdibenzo[b,f]-s-triazo1o[4,3-d]- [1,4]diazepine Amixture of 5,10-dihydro-11H-dibenzo[b,el[l,4- ldiazepine-l 1-thioneprepared as described above (4.2 g; 0.0186 mole) and acethydrazide (13.8g.; 0.186

mole) was kept in a preheated oil bath for 50 minutes at 200 C. using atake'off condenser. It was cooled, water and chloroform were added andthe suspension was filtered; 3.75 g. (81% yield) of 3-methyl-9H-dibenzo[b,f]-s-triazolo{4,3d][1,4]-diazepine of melting point 330 C. wasobtained which did not change on crystallization from tetrahydrofuran.

Anal. calcd. for C H, N C, 72.56; H, 4.87; N, 22.57. Found: C, 72.05; H,4.66; N, 22.81.

EXAMPLE 2 9H-Dibenzo[ b,f] s-triazo1o[4,3-d][ 1,4ldiazepine 1n themanner given in Example 1, 5,10-dihydro-11Hdibenzolb,e][1,4}diazepine-11-thione was condensed at about 200 C.with formic acid hydrazide to give9H-dihenzolh,f1-s-triazo1o[4,3-d][1.4]diazepine of melting point 283-285C.

EXAMPLE 3 6,12-dichloro-9H-dibenzoib.f]-s-triazolo-[4,3- d 1.4ldiazepine In the manner given in Example l. 2,8-dichloro-5,ldihydro-llH-dibenzol b.e l .4ldiazepine-l l-thione was condensed at about 200 C.with formic acid hydrazide to give6,12-dichloro-9H-dibenzoIb.fl-striazolo-[ 4,3-d][ l,4]diazepine.

EXAMPLE 4 In the manner given in Example I, 7-chloro-5.l0- dihydro-llH-dibenzo[b,e][1,4]diazepine-l l-thione was condensed at 200 C. withacethydrazide to give 7-chloro-3-methyl-9H-dibenzo[b,f]-s-triazolo[4.3-

d][ l ,4ldiazepine of melting point 309-3 10.

EXAMPLE 5 In the manner given in Example 1, 3,7-difluoro-5,l0- dihydro-ll H-dibenzo{b,e] 1 ,41diazepine-l l-thione was condensed at about 200 C.with acethydrazide to give 3-methyl-7,ll-difluoro-9H-dibenzo[b,f]-striazolo[4,3-d]-[ l ,4 ldiazepine.

EXAMPLE 6 7. l 0-dinitro-3-[ 3-( dimethylamino )propyl1-9H-dibenzo[b,f]-s-triazolo[4,3-d 1.4 ]diazepine In the manner given inExample 1, 4.7-dinitro-5,l0- dihydro-l lH-dibenzo{b,e][ l.4]diazepine-ll-thione was condensed at about 200 C. with 4- (dimethylamino)butyricacid hydrazide to give 7,10- dinitro-3-[S-(dimethylamino)propyll-(9H)-dibenzo[b.f]-s-triazolo[4,3-d][ l ,4]diazepine.

EXAMPLE 7 Sodium hydride (0.2l g.; 5 moles of 57% dispersion in mineraloil) was added to a solution of 3-methyl-9H-dibenzo[b.f]s-triazolo[4,3-d]ll,4]diazepine (1.24 g.; Smmoles) in 50 ml.of dimethylformamide. the mixture was stirred at room temperature for 25minutes and then heated at 95 C. for 25 minutes. After another l5minutes at room temperature, 3- (dimethylamino)propyl chloride (0.65 g;Smmoles in 0.65 g. of xylene) was added and the mixture was heated at 95C. for 21 hours. It was evaporated and the residue shaken with 25 ml.each of ether and water. The resulting suspension was filtered to give016 g. of starting compound. The filtrate was separated into layers. Theaqueous layer was extracted with methylene chloride (2 X 20 ml.) and thecombined organic extract was washed with saturated salt solution. driedover anhydrous magnesium sulfate and evaporated. The residue wastriturated with ether to give 0.38 g. of 9-{3-(dimethylaminolpropyll-3-methyl-9H-dibenzo[bfl-striazolo[4,3-d][l.4]diazepine of melting point l65-l67 C.. raised to l70.5l7l.5 onrecrystallization from ethyl acetate.

Anal. calcd. for C H N C, 72.04; H. 6.95; N. 21.01. Found: C. 71.82; H.7.29; N. 2l.l2.

EXAMPLE 8 In the manner given in Example 7. 3-methyl-9H-dibenzo[b.f]-s-triazolo[4.3-d][l.4]diazepine was first reacted withsodium hydride and then with 2- (dimethylaminoethyl )chloride to give 9[2- (dimethylamino )ethyl l-3-methyl-9H-dibenzolb.f]-striazolo{4.3-d][l,4]diazepine of melting point 2l5-216 C.

EXAMPLE 9 9-[ 2-( dimethylamino )ethyl 1-9H-dibenzol bf]-striazolo[4,3-d][ l ,4]diazepine In the manner given in Example 7,9H-dibenzo[b.f]- s-triazolo[4,3-d][l,4]diazepine was first reacted withsodium hydride and then with 2-(dimethylamino)ethyl chloride to give9-[2-(dimethylamino)ethyl]-9H- dibenzo[b.f]-s-triazolo[4.3-d][l.4]diazepine of melting point l37138 C.

EXAMPLE l0 9-[ 3-(dimethylamino)propyll-9H-dibenzol bf] -striazolo[4.3-d][ l .4]diazepine In the manner given in Example 7.9H-dibenzo[b,f]- s-triazolo[4,3-d][l,4]diazepine was first reacted withsodium hydride and then with 3- (dimethylamino)propyl chloride to give9-[3- (dimethylamino)propyl]-9H-dibenzo[b,f]-striazolo[4.3-d][l,4]diazepine of melting point l34.5l36.

EXAMPLE 1] 7-Chloro-9-[ 3-(dimethylamino )propyl l-3-methyl-9H- dibenzo[b,f]-s-triazolo[4,3-d][ 1 ,41diazepine In the manner given in Example 7,7-chloro-3- methyl-9H-dibenzolb,f1-s-triazolo[4,3' di][l,4]diazepine wasfirst reacted with sodium hydride and then with 3-(dimethylamino)propylchloride to give 7-chloro-9-[ 3-(dimethylamino )propyl -3-methyl-9I-l-dibenzo[b,f]-s-triazolo[4.3-d]- [l,4]diazepine of meltingpoint l18l C.

EXAMPLE 12 l l-Hydrazino-5l-I-dibenzo{b,e]I 1,4]diazepine hydrochlorideTo a stirred solution of 5,l0-dihydro-l lH-dibenzo-[b,e][l,4]diazepine-l l-thione (42.1 g., 0.0l86 mole) in dry methanol(1,500 ml.) was added hydrazine hydrate (37.4 g., 0.743 mole, A nitrogenbubbler was used to aid in the removal of the hydrogen sulfide formed.The reaction mixture was refluxed via steam bath for l /2 hours andconcentrated in vacuo. The oil was mixed with water and extracted withbenzene. The benzene was washed with water several times, then acidifiedwith aqueous hydrogen chloride. The hydrochloride salt was collected byfiltration, washed with benzene and dried to give 37.0 g. (77% whichsoftens at l35l40 then completely melts at 25 l254. The aqueous layer ofthe filtrate was made basic with aqueus sodium hydroxide and extractedwith chloroform. The chloroform was washed with water, dried (sodiumsulfate) and concentrated in vacuo. The oil was dissolved in ethylacetate and acidified with ethanolic hydrogen chloride to give 2.42 g.,melting point 250 454 and I.31 g.. melting point 260268 of additionalproduct (overall yield 84%). The analytical sample had a melting point253-255.

Anal. calcd. for C H N Cl: C. 59.88; H. 5.03; N. 21.49; CI. 13.60.Found: C. 58.02; H. 5.01; N, 21.20; CI. I3.I3.

EXAMPLE I3 I I-( I-chIoroacetylhydrazinQ-yl)-SH-dibenzo-[b.e][1,4]diazepine hydrochloride lI-Hydrazino-H-dibenzo[b,e]I1.4]diazepine hydrochloride (1.3 g., 0.005mole) was dissolved in water made basic with sodium hydroxide (aqueous),extracted with chloroform. washed with water. dried over sodium sulfateand concentrated. The oil obtained was dissolved in ml. drytetrahydrofuran and cooled in an ice bath. Chloroacetyl chloride (0.56,g.; 0.005 mole) was mixed with 5 ml. of tetrahydrofuran and added slowlyto the reaction mixture. A gummy solid appeared which formed aprecipitate after stirring for one hour. The mixture was cooled and thenstirring continued for 2 hours. The reaction flask was filtered, washedwith chloroform, and then ether. The solid ob tained was dried and usedwithout further purification.

EXAMPLE l4 3ChIoromethyI-9H-dibenzo[ b.f]-s-triazolo-[ 4.3- d][1.4]diazepine I I-( l-chloroacetylhydrazin-Z-yl)-5H-dibenzo[b,e]-[I,4]diazepine hydrochloride (L39 g.. 0.004 mole) was mixed with aceticacid and refluxed under nitrogen at I23 in an oil bath. The reaction wasstirred for minutes, concentrated in vacuo and then diluted with water.The aqueous solution was neutralized with sodium bicarbonate andextracted with chloroform (precipitate is insoluble in chloroform).Methanol was added and the precipitate went into the chloroform layer.The chloroformmethanol layer was washed with water and then with brine,dried over sodium sulfate and concentrated. The solid was crystallizedfrom chloroform methanol and ethyl acetate to give 0.47 g. of 3-chloromethyI-9H-dibenzo[b,f]-s-triazolo[4,3- d][l,4]diazepine of meltingpoint 280-295". Further crops of 0.36 g. and 0.IO5 g. were obtained.

Anal. calcd. for C =,H,,N Cl: C. 63.72; H. 3.92; N. [9.82; CI, I254.Found: C. 633i; H, 3.98; N. I967: CI. I272.

EXAMPLE l5 9 [2-(Diethylamino )ethyl]-3-methyl-9H-dibenzo[ bf]-s-triazolo[4.3-d][1.4]diazepine In the manner given in Examplb 7.3-methyI-9H- dibenzolb.f]-striazoIo[4.3-d]{ l.4]diazepine was reactedwith sodium hydride and then with diethylaminoethyl bromide to give9[2-(diethylamino)ethyl]-3- methyl-9H-dibenzo[b,f]-s-triazolo[4.3-

EXAMPLE I6 6 lZ-Dichloro-J-lZ-(dipropylaminoJethyl]-3methyl-9H-dibenzo[b,f]-s-triazolol4.3-a]|1,4]diazepine In the manner given inExample 7. 6.12-dichloro-9H-dibenzolb.f]-s-triazolo[4,3-d][1.4]diazepine was re acted with sodiumhydride and then with (Z-dipropylaminoethyl)chloride to give6.l2dichloro 12 9-[2-(dipropyIamino)ethyl]-3-methyl-9H-dibenzo[b,fI-s-triazolo[4,3-d]-[l ,4ldiazcpine EXAMPLE l7 7,]l-Difluoro-9-ethyl-3-methyI-9H-dibenzo-[b,fl-striazolo[4,3-d] [1,4idiazepine In the manner given in Example 7,7.1I-difluoro-3-methyI-9H-dibenzo[b,fl-s-triazolo[4,3-dl [l ,4]diazepin was reacted withsodium hydride and then with ethyl iodide to give 7,]I-difluoro-9-ethyl-3-rnethyl-9H- clibenzo[b,f]-s-triazolo[4,3-d][1,41diazepine.

EXAMPLE l8 7-Chloro-3,9-bis[2-(dimethylamino)ethyl]9H-dibenzo [b,fI-s-triazolo[4,3-dl [I ,4]diazepine In the manner given in Example 7,7-chloro-3-[2- (dimethylamino)ethyl]-9H-dibenzo[b,fJ-s-triazolo[4,3-d]-[I,4]diazepine was reacted with sodium hydride and then with2-(dimethylamino)ethyl bromide to give7-chl0ro-3,9-bis{2-(dimethylamino)ethyl]-9H-dibenzo[b,fl-s-triazolo[4,3-d] [l ,4]diazepine EXAMPLE 19 EXAMPLE 203-diethylamino-9Hdibenzo[b.fl-s-triazolo-[4,3- dl [I .4]diazepine Amixture of 3-bromo-9H-dibenzo[b.f]-s-triazolo- [4,3-d}[l.4]diazepine anddiethylamine was refluxed for 18 hours and then poured into water. Themixture was made alkaline with sodium bicarbonate and then extractedwith chloroform. After evaporation of the chloroform extracts3-diethylamino-9H-dibenzo[b.fls-triazolo[4.3d]-[I.4Idiazepine wasobtained which was purified by crystallizations from ethanolwater.

EXAMPLE 21 3-Cyanomethyl-9H-dibenzo[b,fl-s-triazolo-[4,3- d][ 1,4ldiazepine 3 -Chloromethyl -9H -dibenzo[b,f] -s-triazolo[4,3 -d]-[1,41diazepine was added, under nitrogen to a stirred solution of sodiumcyanide in dry dimethylsulfoxide which had been warmed in a bathmaintained at 84 C. After 30 minutes the mixture was cooled, and pouredinto water; the product was extracted with chloroform.

The extract was washed with brine, dried over anhydrous potassiumcarbonate and concentrated. The residue was crystallized from ethylacetate-Skellysolve B hexanes to give3-cyanomethyl-9H-dibenzo[b,f]-s-triazolo[4,3-d]- [1,4]diazepine.

EXAMPLE 22 3-Cyano-9H-dibenzoIb,f]-s-triazolo[4,3-d]- 1,4]diazepine Inthe manner given in Example 21, 3-chloro-9H- dibcnzo[b,f]-s-triazolo[4,3-d][ 1,4]diazepine was treated with potassium cyanideto give 3-cyano-9H- dibenzo[b,f}-s-triazolo[4,3-d][1,4]diazepine1EXAMPLE 23 9H-Dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepin3- acetic acidmethyl ester A mixture of3-cyanomethyl-9H-dibenzo[b,f]-striazolo-[4,3-d][1,41diazepine, methanoland ether was cooled in a salt-ice bath and the reaction mixturesaturated with a stream of anhydrous hydrogen chloride during 15minutes. The mixture was allowed to warm slowly to ambient temperatureand stand for 18 hours. It was then poured into water, neutralized withsodium bicarbonate and extracted with chloroform. The extract was washedwith brine, dried and concentrated. The residue was crystallized frommethanolethyl acetate to give 9H-dibenzo[b,f]-s-triazolo-[4,3-d][1,4]diazepin-3-acetic acid methyl ester.

EXAMPLE 24 6,12-Dichloro-3-I l-methylpiperidin-2-yll-9H-dibenzo[b,f]-s-triazolo[4.3-dl[ l ,41diazepine In the manner given inExample 1, 2,8-dichloro-5,10- dihydro-l lH-dibenzo[b,el{1,4]diazepine-ll thione was condensed with l-methyl-2-piperidinyllformic acid hydrazideat about 200 C. to give 6.12-dichlorc- 3-[l-methylpiperidin-2-yl]-9H-dibenzo[b,f]-striazolo[4.3-d][1,4]diazepine.

EXAMPLE 25 14 Anal. calcd. for C H N C, 70.08; H, 5.88; N, 24.04. Found:C, 70.40; H, 5.84; N, 24.51.

EXAMPLE 26 3-[ (Diethylamino )methyll-9H-dibenzolb,f]-striazolo[4.3-d][1,4]diazepine To a stirred solution of3-chloromethyl-9H-dibenzo- [b.f]-s-triazolo[4,3-d][1,4]diazepine (1.41g., 0.005 mole) in dry tetrahydrofuran (25 ml.) and methanol (5 ml.) wasadded potassium iodide 1.66 g.) and diethylamine (5 ml.) under nitrogen.The mixture was stirred at ambient temperature for 2 hours, mixed withwater and extracted with chloroform. The chloroform solution was washedwith water, dried over sodium sulfate and concentrated in vacuo. The oilwas crystallized from methanol-chloroform-ethyl acetate to give 1.35 g.of 3-[(diethylamino)methyl]-9H-dibenzo[b,f]-s-triazo1o[4,3-d][1,4]diazepine of melting point 232-235. The analyticalsample had a melting point of 23223S.

Anal. calcd. for C, H ,N C, 71.44; H, 6.63; N, 21.93. Found: C, 70.95;H, 6.70; N, 21.51.

EXAMPLE 27 3-( Pyrrolidinomethyl l-9H-dibenzol b,f]-s-triazolol 4,3- d][1,4]diazepine To a stirred solution of 3-chloromethyl-QH-dibenzo-[b,f]-s-triazolo[4,3-d][1,4]diazepine (1.41 g., 0.005 mole) in drytetrahydrofuran (20 ml.) and methanol (5 ml.) was added potassium iodide1.66 g.) and pyrrolidine (5 m1.) under nitrogen. The mixture was stirredat ambient temperature for 2 hours, mixed with water and extracted withchloroform. The chloroform was washed with water, dried over sodiumsulfate and concentrated in vacuo. The oil was crystallized frommethanol ethyl acetate to give 1.26 g. (80%), of melting point 107 of3-(pyrrolidinomethyl)-9H- dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine.The analytical sample had a melting point of 100-107 (foaming).

Anal. calcd. for C, H N,=,: C, 71.90; H, 6.03; N, 22.07. Found: C,71.63; H, 6.26; N, 22.06.

EXAMPLE 28 3-( 2-Chloroethyl )-9H-dibenzo[ b,f]-s-triazolo- 4,3- d][1,4]diazepine 11-Hydrazino-5H-dibenzo[b.e][1,4]diazepine hydrochloride(13.0 g., 0.05 mole) was dissolved in water, neutralized with aqueoussodium hydroxide and extracted with chloroform. The chloroform waswashed with water, dried over sodium sulfate and concentrated in vacuo.The oil was dissolved in dry tetrahydrofuran (200 ml.), under nitrogenand 3-chloropropionyl chloride (6.35 g., 0.05 mole) in tetrahydrofurn(50 ml.) was added slowly to the stirred solution. The reaction mixturewas stirred at ambient temperature for 2 /2 hour. The hydrochloride saltof the adduct was collected by filtration, washed with ether and driedin a vacuum oven (40 to give 1.431 g.

This hydrochloride salt was combined with glacial acetic acid 150 ml.)and heated, under nitrogen in an oil bath at for 15 minutes. Thereaction mixture was cooled and the precipitate collected by filtrationand washed with acetic acid. The precipitate was mixed with water andchloroform, neutralized with aqueous sodium hydroxide and recollected byfiltration. The

chloroform was separated, washed with water, dried over sodium sulfateand concentrated in vacuo. These two residues were recrystallized frommethanol chloroform ethyl acetate to give 4.37 g. (37% melting point90-92 of 3-( 2-chloroethyl )-9H-dibenzolb.f]-striazolo{4,3-dl[1,4]diazepine. The analytical sample had a meltingpoint of 9497.5.

Anal. calcd. for C,,,H -,N ,Cl: C, 64.75; H. 4.41; N, 18.88; Cl, 11.95.C, 65.88: H, 4.39; N, 19.90; Cl. 10.49.

EXAMPLE 29 To a stirred solution of 3-(2-chloroethyl)-9H-dibenzo-[b,fl-s-triazolo[4,3-d][1,4]diazepine (1.48 g., 0.005 mole) indry dimethylformamide (25 ml.) was added potassium iodide (1.66 g.) anddimethylamine (4.745 g., in 5 ml. methanol) under nitrogen. The mixturewas stirred at ambient temperature for 18 hours, mixed with water andextracted with chloroform. The chloroform was washed with water, driedover sodium sulfate and concentrated in vacuo. The oil was crystallizedtwice from methanol ethyl acetate to give 0.48 g. of3-12-(dimethylamino)-ethyl]-9H-dibenzo[b,f]-striazolo[4,3-d][1,4]diazepine,(32%), melting point 161-165. The analytical sample had a melting pointof l61l65.

Anal. calcd. for C H N C, 70.79; H, 6.27; N, 22.94. Found: C, 70.70; N,6.33; N, 23.11.

EXAMPLE 30 To a stirred solution of 3-(2-chloroethyl)-9H-dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine (1.48 g., 0.005 mole) indry dimethylformamide (25 ml.) was added potassium iodide (1.66 g.) andpyrrolidine (5 ml.) under nitrogen. The mixture was stirred at ambienttemperature for 18 hours mixed with water, dried over sodium sulfate andconcentrated in vacuo. The oil was crystallized twice from methanolethyl acetate to give 071 g. (43%) of 3-(2-pyrrolidinoethyl)-9Hdibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine of melting point 2082 Theanalytical sample had a melting point of 2082l0.

Anal. calcd. for C H ,N

C. 72.48; H, 6.39; N, 21.13. Found: C, 72.96; H,

EXAMPLE 31 3-Vinyl-9H-dibenzo[b,f]-s-triazolo[4,3-d]-[1,4]- diazepine.

To a stirred solution of 3-(2-chloroethyl)-9H-dibenzo-[b,f]-s-triazolo[4,3-d][1,4]diazepine (1.26 g., 0.00425 mole) indry dimethylformamide (25 ml.) was added potassium iodide (1.66 g.) anddiethylamine (5 ml.) under nitrogen. The mixture was stirred at ambienttemperature for 18 hours, mixed with water and extracted withchloroform. The chloroform was washed with water, dried over sodiumsulfate and concentrated in vacuo. The residue was collected, washedwith ethyl acetate and recrystallized from methanol-ethyl acetate togive 0.545 g. (38%) of3vinyl-9H-dibenz0[b,f]-striazolol4.3-d][1,4]diazepine of melting point300". The analytical sample had a melting point of 300.

Anal. calcd. for C, H, N C, 73.82; H, 4.65; N, 21.53. Found: C, 73.40;H, 4.69; N, 20.79.

EXAMPLE 32 3-( 3-Chloropropyl )-9H-dibenzo[ b,f]-s-triazolo-l4,3- d][1,4]diazepine 1 l-Hydrazino-SH-dibenzolb,e][1,4]diazepine hydrochloride13.08 g., 0.05 mole) was dissolved in water. neutralized with aqueoussodium hydroxide and extracted with chloroform. The chloroform waswashed with water, dried over sodium sulfate and concentrated in vacuo.The oil was dissolved in dry tetrahydrofuran 150 ml.) under nitrogen and4-chlorobutyryl chloride (7.05 g., 0.05 mole) in dry tetrahydrofuran (50ml.) was slowly added to the stirred solution. The reaction mixture wasstirred at ambient temperature for 4 hours. The hydrochloride salt ofthe adduct was collected by filtration, washed with ether and dried in avacuum oven (40) to give 14.123 g.

This hydrochloride salt was combined with glacial acetic acid ml.) andheated under nitrogen in an oil bath at for 15 minutes. The reactionmixture was cooled and the precipitate collected by filtration andwashed with acetic acid. The filtrate was concentrated in vacuo, mixedwith water, neutralized with aqueous sodium hydroxide and extracted withchloroform. The collected precipitate from above was mixed with waterand chloroform, neutralized with aqueous sodium hydroxide and thechloroform separated. The two chloroform solutions were combined, washedwith water, dried over sodium sulfate and concentrated in vacuo. Theresidue was dissolved in methanolchloroform decolorized with Dorco andcrystallized by concentrating and adding ethyl acetate to give 8.76 g.of 3-(3-chloropropyl)-9H-dibenzo[b,f]-s-triazolo(4,3- d][1,4]diazepineof melting point 177 and 2.28 g., melting point l7ll72 (overall yield92%). The analytical sample had a melting point of 173l75" C.

Anal. calcd for C, H, =,N Cl: C, 65.69; H, 4.86; N, 18.03; Cl, 11.41Found: C, 65.38; H, 5.00; N, 18.04; C], 1 1.60.

EXAMPLE 33 3-13-(Dimethylamino)propyl]-9H-dibenzo[b,f]-striazolo{4,3-d][1,4]diazepine dihydrochloride To a stirred solution of3-(3-chloropropyl)-9H- dibenzolb.f]-s-triazolo{4,3-d][1,4]diazepine(1.55 g., 0.005 mole) in dry dimethylformamide (25 ml.) was addedpotassium iodide (1.66 g.) and dimethylamine 15 ml. of a saturatedmethanol solution) under nitrogen. The mixture was stirred at ambienttemperature for 40 hours and at 50 for 18 hours to complete thereaction. The mixture was mixed with water and extracted withchloroform. The chloroform was washed with water. dried over sodiumsulfate and concentrated in vacuo. The oil was dissolved in ethylacetate aciditied with methanolic hydrogen chloride and recrystallizedfrom methanol ethyl acetate to give 1.74 g. of 3- [3-dimethy lamino)propyl ]-9H-dibenzo[b,f]-striazo1o[4.3-d][l.4ldiazepine dihydrochloride(94%) of melting point 290-293. The analytical sample had a meltingpoint of 29l296.

Anal. calcd. for C H N Cl i C, 55.13; H. 6.80; N, 1891; C1. 19.15.Found: C, 57.47; H, 5.90; N, 17.89; Cl. 17.99.

EXAMPLE 34 3-[ 3-( diethylamino )propyl]-9H-dibenz0[b,f]-striazolo[4,3-dl[ 1 ,41diazepine dihydrochloride To a stirredsolution of 3 (3-Chloropropyl)-9H-dibenzo[b,f]-s-triazol[4,3-dl[1,4]diazepine (1.55 g., 0.005 mole) in drydimethylformamide (25 ml.) was added potassium iodide (1.66 g.) anddiethylamine m1.) under nitrogen. The mixture was stirred at ambienttemperature, mixed with water and extracted with chloroform. Thechloroform was washed with water, dried over sodium sulfate andconcentrated in vacuo. The oil was dissolved in ethyl acetate, acidifiedwith methanolic hydrogen chloride and recrystallized from methanol-ethylacetate to give 1.30 g., of 3-[3-(diethylamino)propyl]-9H-dibenzo[b,f]-s-triazolo[4,3- d][1,4]diazepinedihydrochloride of melting point 278-283 and 0.21 g., of melting point275285 (overall yield 72%). The analytical sample had a melting point of275-280.

Anal. calcd. for C H N Cl C, 59.99; H, 6.47; N, 16.66; C1, 16.87. Found:C, 59.32; H, 6.37; N, 16.10; Cl, 16.65.

EXAMPLE 35 3-( 3-Pyrrolidinopropyl )-9H-dibenzo[ b,f]-striazolo[4,3-d][1,4]diazepine dihydrochloride To a stirred solution of3-(3-chloropropyl)-9H- dibenzo[b,f]-s-triazolo[4,3-d]{1,4]diazepine(1.55 g., 0.005 mole) in dry dimethylformamide (25 ml.) was addedpotassium iodide (1.66 g.) and pyrrolidine (5 ml.) under nitrogen. Themixture was stirred at ambient temperature for 40 hr., mixed with waterand extracted with chloroform. The chloroform was washed with water,dried over sodium sulfate and concentrated in vacuo. The oil wasdissolved in ethyl acetate, acidi fled with methanolic hydrogen chlorideand recrystallized from methanol-ethyl acetate to give 1.65 g. of 3-(3-pyrrolidinopropyl)-9H-dibenzo-[b,f]-s-triazolo[4,3- d][1,4]diazepinedihydrochloride of melting point 285-290 (overall yield 91%). Theanalytical sample had a melting point of 295-300.

Anal. calcd. for C ,H N Cl C, 60.28; H, 6.02; N, 16.74; C1, 16.95.Found: C, 59.80; H, 5.93; N, 17.04; Cl, 16.85.

In the manner illustrated in the preceding examples, other compounds offormula 111 are obtained, such as:

7,1 l-difluoro-3,9-bis[(dimethylamino)methyll-9H-dibenzo-[b,f]-s-triazolo[4,3-d][1,4]diazepine;

6,12-dichloro-3-bromo-9H-dibenzo[b,f]-striazolo[4,3-d]-[1,4]diazepine;

6,1 2-diisopropoxy-3-methyl-9-ethyl-9H-dibenzo[b,f]-

s-triazolo[4,3-d][1,4]diazepine;

7,1 O-dibromo-3,9-dipropyl-9H-dibenzolb,f]-s-triazolo- [4,3-d][1,4]diazepine;

l 1-trifluoromethyl'7bromo-3-isopropyl-9H-dibenzo[b,fl-s-triazolo[4,3-d][1,4]diazepine;

l3ch1oro-3-( 2-pyrrolidino )ethyl-9H-dibenzolb,f]-striazolo[4,3-d][1,4]diazepine;

l 1-isopropyl-3-(3-morpholinopropyl)-9H-dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine;

12-chloro-3,9-bis( morpholinomethyl )-9H-dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine;

l l-bromo-3,9-dimethyl-9H-dibenzolb,f]-striazolo[4,3-d]-l ,41diazepine;

3-hydroxymethyl-9-( 2-( dimethylamino )ethyl ]-9-dibenzo-[b,f]-s-triazolo[4,3-d][1,4]diazepine;

3-hydroxymethyl-7-ch1oro-9H-dibenzol b,f]-s-triazolo-[4,3-d][1,4]diazepine;

7-chloro-3-[ 2-( 4-ethylpiperazino )ethyl ]dibenz0[b,f]-striazolo[4,3-d][ l ,41diazepine;

3-[ 2-( 4-methy1piperazino )propyl ]dibenzo[b,f]-striazolo-[4,3-d1[1,4]diazepine;

and the like.

Treating the compounds of formulae 1] or 111 with a pharmacologicallyacceptable acid such as hydrochloric, hydrobromic, phosphoric, sulfuric,acetic, propionic, toluenesulfonic, methanesulfonic, tartaric, citric,lactic, malic, maleic, cyclohexanesulfamic and the like produces thepharmacologically acceptable salts of these compounds of formula 11 or111 which can be used like the free base compounds of formula 11 or 111.

Salt formation is achieved in conventional manner by reacting thecompounds of formula 11 or 111 with excess of a selected acid in asuitable medium e.g. water, a lower alkanol, ether, or acetone andrecovering the salt by evaporating the solvent, preferably in vacuo.

The N-oxides are prepared by reacting the compounds of formula 11 or 111with an excess of a peracid such as perbenzoic acid, perphthalic acid,or mchloroperbenzoic acid, in a solvent such as a lower alkanol,chloroform, or methylene chloride and recovering the N-oxide byevaporating the solvent in vacuo.

We claim: 1. A compound selected from the group consisting of compoundsof the formula lll wherein R is selected from the group consisting ofhydrogen, alkyl of l to 3 carbons, inclusive in which n is l to 4,inclusive, and R is hydrogen or alkyl defined as above, or R is in whichn is defined above, r; and R, are each selected from the groupconsisting of hydrogen and alkyl as defined above, or

together is pyrrolidino, or piperidino; wherein R is selected from thegroup consisting of hydrogen, alkyl defined as above, hydroxymethyl,

in which n is 0 to 4, inclusive, and R is hydrogen or alkyl defined asabove. or R is in which n is defined above, R and R are each selectedfrom the group consisting of hydrogen and alkyl as defined above, or

/R7 or -N wherein R is selected from the group consisting of hydrogen.methyl, ethyl,

in which rz is I to 3 inclusive; R is hydrogen or alkyl of l to 3 carbonatoms, inclusive; or R is in which n, is defined as above, R and R areselected from the group consisting of hydrogen and alkyl as de finedabove, or, together is pyrrolidino or piperidino; wherein R is selectedfrom the group consisting of hydrogen, alkyl, as defined above,

in which n is O to 3, inclusive, and R and R are each selected from thegroup consisting of hydrogen and alkyl as defined above, or

IR? or -N together is pyrrolidino or piperidino; wherein R' and R' areselected from the group consisting of hydrogen, fluoro, bromo, chloro,nitro, and the pharmacologically acceptable acid addition salts thereof3. A compound according to claim 1 of the formula 1118 lllB wherein R"is hydrogen, methyl, ethyl or R (m m N R I a in which n is l to 3,inclusive, and R, and R' are hydrogen, methyl or ethyl, or

21 together is pyrrolidino; wherein R", is hydrogen, methyl, ethyl,

in which n is defined as above, and R", and R",, are each selected fromthe group consisting of hydrogen, methyl and ethyl; wherein R",, andR",, are selected from the group consisting of hydrogen, fluoro andchloro, and the pharmacologically acceptable acid addition saltsthereof.

4. A compound according to claim 3 wherein R", is methyl, R",, R",, andR",, are hydrogen, and the compound therefore is3-methyl-9H-dibenzo[b,f]-striazolo[4,3-d]-[1,4]diazepine.

5. A compound according to claim 3 wherein R", is

R", is methyl, R",, and R", are hydrogen and the compound is therefore9-[3-(dimethylamino)propyl]-3- methyl-9H-dibenzo[b,f]-s-triazolo[4,3- d]l ,4]diazepine.

6. The compound of claim 3, wherein R", is (dimethylamino)ethyl, R", ismethyl, R",, and R",, are hydrogen and the compound is therefore 9-[2-(dimethylamino)ethyl]-3-methyl-9H-dibenzo[b,f]-striazolo[4,3-d][1,4]diazepine.

7. The compound of claim 3, wherein R", is dimethylaminoethyl, R",, R",,and R", are hydrogen and the compound is therefore9-[2-(dimethylamino)ethyl]-9H-dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine.

8. The compound of claim 3, wherein R", is dimethylaminopropyl, R",, RR",, are hydrogen and the compound is therefore9-[3-(dimethylamino)propyl]-9H-dibenzo[b,f]-s-triazolo[4,3-d][1,4]diazepine.

9. The compound of claim 3, wherein R, is 3- dimethylaminopropyl, R", ismethyl, R",, is hydrogen,

- CH CH CH R", is 7-chloro and the compound is therefore 7-chloro-9-3-{(dimethylamino)propyl1-3-methyl-9H- dibenzolbfls-triazolol4,3-d][ 1,4}diazepine.

10. The compound of claim 3, wherein R",, R",, R",,, and R", arehydrogen and the compound is therefore9H-dibenzo-[b,f]-striuzolo[4,3-d]l l ,4]diazepine.

11. The compound of claim 3, wherein R", is methyl, R", and R",, arehydrogen, R, is 7-chloro, and the compound is therefore7-chloro-3-methyl-9H- dibenzol'b,fls-triazolo{4,3-d][ l ,4]diazepine.

12. The compound of claim 3 as dihydrochloride, wherein R" isB-(diethylamino)propyl, R",, R",,. and R", are hydrogen and the compoundis therefore 3-[ 3-(diethylamino)propyl]-9H-dihenzo[b,f]-s-triazolo[4,3- d][ l,4]diazepinedihydro-chloride.

l3. 3-(chloromethyll-9H-dibenzo[b,fl striazolo[4,3-d]-[1,4]dia2epine.

14. The compound of claim 3, wherein R" is (diethylarnino)methyl, R",R",,, and R", are hydrogen and the compound is therefore 3-[(dimethylamino)methyl]-9H-dibenzo[b,f]-striazolo{4,3-d][1,4]diazepin.

15. The compound of claim 3 wherein R", is (die thylamino)methyl, R",,R",,, and R", are hydrogen and the compound is therefore 3-[(diethylamino)methyl]9H-dibenzo [b,f] s triazolo[4,3-d][ l,4]diazepine.

16. The compound of claim 2, wherein R' is pyrrolidino, methyl, R',, R,R, are hydrogen and the compound is therefore 3-(pyrrolidinomethyl)-9H-dibenzo[b,f]-s-triazolo[4,3-d]l1,4]diazepine 18. The compound of claim 3wherein R" is 2- (dimethylaminokthyl, R",, R",, and R", are hydrogen andthe compound is therefore 3-[2-(dimethylamino)ethyl]9H-dihenzo[b,f]striazolo[4,3-d][ l ,4]diazepine.

19. The compound of claim 2, wherein R' is 2- (pyrrolidinyUethyl, R',,R-,, and R, are hydrogen and the compound is therefore3-[2(pyrrolidinyllethyH- 9Hdibenzo[h,f]-s-triazolo[4,3-dll l,41dia2epine.

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THEFORMULA III
 2. A compound according to claim 1 of the formula
 3. Acompound according to claim 1 of the formula IIIB
 4. A compoundaccording to claim 3 wherein R''''2 is methyl, R''''1, R''''3, andR''''4 are hydrogen, and the compound therefore is3-methyl-9H-dibenzo(b,f)-s-triazolo(4,3-d)-(1,4)diazepine.
 5. A compoundaccording to claim 3 wherein R''''1 is
 6. The compound of claim 3,wherein R''''1 is (dimethylamino)ethyl, R''''2 iS methyl, R''''3 andR''''4 are hydrogen and the compound is therefore9-(2-(dimethylamino)ethyl)-3-methyl-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.
 7. The compound of claim 3, wherein R''''1 isdimethylaminoethyl, R''''2, R''''3, and R''''4 are hydrogen and thecompound is therefore9-(2-(dimethylamino)ethyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.
 8. The compound of claim 3, wherein R''''1 isdimethylaminopropyl, R''''2, R3, R''''4 are hydrogen and the compound istherefore9-(3-(dimethylamino)propyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.
 9. The compound of claim 3, wherein R''''1 is3-dimethylaminopropyl, R''''2 is methyl, R''''3 is hydrogen, R''''4 is7-chloro and the compound is therefore7-chloro-9-3-((dimethylamino)propyl)-3-methyl-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.10. The compound of claim 3, wherein R''''1, R''''2, R''''3, and R''''4are hydrogen and the compound is therefore9H-dibenzo-(b,f)-s-triazolo(4,3-d)(1,4)diazepine.
 11. The compound ofclaim 3, wherein R''''2 is methyl, R''''1 and R''''3 are hydrogen,R''''4 is 7-chloro, and the compound is therefore7-chloro-3-methyl-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1, 4)diazepine. 12.The compound of claim 3 as dihydrochloride, wherein R''''2 is3-(diethylamino)propyl, R''''1, R''''3, and R''''4 are hydrogen and thecompound is therefore3-(3-(diethylamino)propyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)-diazepinedihydro-chloride.
 14. The compound of claim 3, wherein R''''2 is(diethylamino)methyl, R''''1, R''''3, and R''''4 are hydrogen and thecompound is therefore3-((dimethylamino)methyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepin.15. The compound of claim 3 wherein R''''2 is (diethylamino)methyl,R''''1, R''''3, and R''''4 are hydrogen and the compound is therefore3-((diethylamino)methyl)-9H-dibenzo-(b,f)-s-triazolo(4,3-d)(1,4)diazepine.16. The compound of claim 2, wherein R''2 is pyrrolidino, methyl, R''1,R''3 R''4 are hydrogen and the compound is therefore3-(pyrrolidinomethyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1, 4)diazepine.18. The compound of claim 3 wherein R''''2 is 2-(dimethylamino)ethyl,R''''1, R''''3, and R''''4 are hydrogen and the compound is therefore3-(2-(dimethylamino)ethyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.19. The compound of claim 2, wherein R''2 is 2-(pyrrolidinyl)ethyl,R''1, R''3, and R''4 are hydrogen and the compound is therefore3-(2-(pyrrolidinyl)ethyl)-9H-dibenzo(b,f)-s-triazolo(4,3-d)(1,4)diazepine.